JPH08137056A - Manufacture of solid processing agent for silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide a method for manufacturing a solid processing agent for a silver halide photographic material, by which, when a composition containing thiosulfate, sulfite, bisulfite, a ferric salt of aminopolycarboxylic acid, carbonate, a paraphenylenediamine color developing agent, or hydroxylamine and its derivative, is granulated by means of a fluidized-bed granulator and compression molding is performed using the granulated powders obtained, the amount of packing does not vary, wear and expansion of the agent when it is in a tablet form can be prevented effectively, and, even if the agent is preserved in granular form, blocking does not occur. CONSTITUTION: In a method for manufacturing a granular solid processing agent for a silver halide photographic material, when powders containing at least one kind selected from among thiosulfate, sulfite, bisulfite, a ferric salt of aminopolycarboxylic acid, carbonate, a paraphenylenediamine color developing agent, hydroxylamine and its derivative, are held fluidized by an air current and are spray granulated by use of bound water, theoretical relative humidity is held at not lower than 15% and not higher than 60%; the granular solid processing agent obtained is compression molded in a compression retention time of not less than 0.02sec and not more than 1.0sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing granular solid processing agents and tablet solid processing agents for silver halide photographic light-sensitive materials.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are
Processing is performed by steps such as development, desilvering, washing and stabilization.
Processing is usually carried out in an automatic processor, and in that case, a replenisher replenishment system is generally widely used to keep the activity of the processing solution in the processing tank constant. A large amount of waste liquid is generated because the product is diluted, the evaporation amount is corrected, and the consumption component is replenished.

On the other hand, in recent years, the movement to regulate the dumping of photographic waste liquid into the ocean and the regulations on the disposal of plastic materials have been strengthened worldwide, and the system for reducing the photographic waste liquid and avoiding the use of plastic bottles for liquid processing agents has been developed. Development is required.

Further, transportation regulations have been increased due to tightened safety regulations for packaging materials for ensuring safety in transportation of liquid dangerous substances, and in minilab stores, which have been rapidly increasing in recent years, advances in exposure control technology for printing. With the introduction of a system that anyone can easily get prints at,
Although there are many places where workers are part-time or part-time workers, it is difficult to dissolve the replenisher and manage the treatment solution as before, and it is easy to make a very serious mistake such as mistakenly dissolving and replenishing the treatment agent. As a result, there have been many complaints about the conventional replenisher replenishment method.

Therefore, in the photographic processing industry, there has been a strong demand for the development of a solid processing agent which does not require a processing agent bottle and which can eliminate manual dissolution work. In order to meet this demand, Japanese Patent Laid-Open No. 5-119454 and the like disclose a method of solidifying almost all the processing agent components and directly charging them into a processing tank.

[0006]

However, in the production of the solid processing agent, there is a problem that productivity, production cost and stable productivity are poor.

[0007] Granules obtained by forced agglomeration granulation with a stirring granulator on a production scale (for example, 80 kg or more in batch) are likely to form coarse particles having a diameter of 5 mm or more. The coarse particles do not easily flow, and when fluidized and dried, the coarse particles become larger together with the surrounding granules. The coarse particles grown in this way have a large internal water content even if the surface is dried, and it takes a long time to dry them, but the granules obtained by performing a long drying operation are very It has been found that the tablet becomes a firm and heavy substance and its solubility deteriorates, and the tablet obtained by compression-molding it becomes too heavy and lacks in hardness, resulting in deterioration of the abrasion loss.

On the other hand, coarse particles can be classified or crushed during the drying process, but the addition of such a step requires a long time for production and significantly reduces the yield. Furthermore, by crushing coarse particles, fine powder unfavorable for tableting is generated, and the particle size distribution is likely to vary, and problems relating to the performance of solid processing agents such as capping during tableting and variation in filling amount. Is likely to occur.

On the other hand, JP-A-3-39739, 3-39735, and
In Examples such as 2-109042, a method for producing a granular solid processing agent using a fluidized bed granulator is disclosed, which is an advantageous production method for making the obtained granules into a final product form. Is the way.

However, a composition containing a thiosulfate, a sulfite, a bisulfite, a ferric aminopolycarboxylic acid salt, a carbonate, a paraphenylenediamine color developing agent, or a hydroxylamine or a derivative thereof is in a fluidized bed. If you try to granulate using a granulator, by storage for a long period of time or under high temperature and high humidity, blocking occurs in the obtained granules, tablets formed by compression molding of the obtained granules do not escape abrasion and expansion, It was found that the granules made into tablets by compression molding are not preferable due to variations in the filling amount.

The present invention has been made under the above circumstances, and its object is to provide a thiosulfate, a sulfite, a bisulfite, a ferric aminopolycarboxylic acid salt, a carbonate, a paraphenylenediamine-based color developing agent. , Or in the case of granulating a composition containing hydroxylamine or a derivative thereof using a fluidized bed granulator, when compression-molding using the obtained granules, there is no variation in the filling amount, and tablets are formed. It is an object of the present invention to provide a method for producing a solid processing agent for a silver halide photographic light-sensitive material, which can effectively prevent abrasion and swelling at the time and does not cause blocking even when stored in a granular state.

[0012]

The above objects of the present invention are thiosulfates, sulfites, bisulfites, ferric aminopolycarboxylic acids, carbonates, paraphenylenediamine color developing agents, hydroxylamines and Halogenation of a theoretical relative humidity of 15% or more and 60% or less when spray granulating a powder or granule containing at least one selected from its derivatives with a water stream in a fluidized state Method for producing granular solid processing agent for silver photographic light-sensitive material, granulation in atmosphere with theoretical relative humidity of 20% or more and 50% or less, two-fluid spraying method, the two-fluid method Gas-liquid ratio of (amount of atomized air supplied per unit time)
When defined as / (volume of bound water supplied per unit time), the gas-liquid ratio is 100 or more and 10000 or less, the gas-liquid ratio is 1000 or more and 5000 or less, Supplying dehumidified air to make it flow, granulating using a granule having a weight average particle size of 20 μm or more and 350 μm or less, the total amount of bound water sprayed with respect to the charged amount of the granule. Content of 1% by weight or more and 50% by weight or less, the concentration of the additive in the bound water is 1% by weight or more and 60% by weight or less, and the granular solid processing agent obtained by these production methods is stagnant in compression. It is achieved by performing compression molding in a time of 0.02 seconds or more and 1.0 seconds or less.

That is, the present inventors contain thiosulfates, sulfites, bisulfites, ferric aminopolycarboxylic acids, carbonates, paraphenylenediamine color developing agents, or hydroxylamine and its derivatives. When the system is granulated in a fluidized bed by supplying bound water, blocking occurs when stored in a granular state due to the fact that these compounds are water-soluble, and the resulting granules were compression-molded. Considering that tablets are inevitably abraded and swelled, and after repeated examinations with various operating factors, it was found that the above problems can be overcome by setting conditions at a specific relative humidity, and the present invention has been achieved. is there.

The present invention will be described in detail below.

The method for producing the granular solid processing agent of the present invention comprises:
It is based on the fluidized bed granulation method. That is, the powder and granules are kept in a fluidized state by an air flow, and a solution containing a binder and the like is sprayed onto the powder and agglomerated by the binding force between the powders to granulate, and the raw materials are mixed, granulated, and dried. The feature is that they can be performed in the same container that is closed. The obtained granules are very porous and have excellent solubility, and are suitable as tablet-forming granules.

In the present invention, the term "powder or granule" refers to a simple substance selected from powder, crystals or granules and a mixture thereof. Granules are granules of powder or fine crystals with a particle size of 53-28.
It refers to 30 μm particles.

The weight average particle diameter of the granular solid processing agent obtained in the present invention is preferably 100 to 600 μm in view of its use.
Here, the weight average particle diameter D uses a plurality of JIS standard sieves,
D = (Σn · d) / Σn, where d is the median of the openings and n is the weight frequency of the particles.

The weight-average particle size of the granules before granulation is 20 to
It is about 350 μm, preferably 50 to 150 μm. That is, 20μ
If it is less than m, the raw material of the photographic processing agent tends to absorb moisture, so that it may not flow uniformly due to blocking or may cause clogging of the filter of the apparatus. If it exceeds 350 μm, the effect of the present invention is deteriorated. When coarse particles are contained in the raw material, it is preferable to pulverize or regulate the size in advance, and a crusher such as a hammer mill, a pin mill, a roll mill or a screen mill or a sizing machine can be used.

FIG. 1 is a schematic view of an example of a fluidized bed granulator, and the process of the manufacturing method of the present invention will be described with reference to this.

The air sucked by the blower fan F is cleaned by an air supply filter E made of chemical fiber or the like, and then heated to a predetermined temperature by a heat exchanger D,
It is sent to the fluid tank body 1 through the flow straightening plate 4. The hot air keeps the particles in a suspended state and makes them uniformly contact with the compressed air B, the liquid feeding device C, and the liquid droplets atomized by the spraying device 3, and at the same time, it is a heat source for the evaporation and drying of the fluidized bed spray-moistened. Acts as. The fine powder scattered on the upper part is collected by the dust collecting filter 2 and is discharged into the fluidized bed. The air filtered here is discharged to the outside of the system by the exhaust fan A.

The air to be supplied may be nitrogen or an inert gas, but is preferably air from the viewpoint of cost, and further, a dehumidifying means should be provided so as not to be affected by the season and weather. preferable. The dust collecting filter is preferably separated into two so that the flow does not have to be stopped during granulation.

The fluidized bed granulator can be easily obtained as a commercial product, specifically, manufactured by Paulec Co .; Multiplex series, GPCG series, WST / WSG series, Fuji Paudal Co., Ltd .; New Malmo Riser series, Okawara Seisakusho Co., Ltd .; Mixgrad series, Freund Sangyo Co., Ltd .; Spiraflow series, Flow coater series, etc.

In the present invention, the theoretical relative humidity means the temperature (t) at the inlet of the air supplied to the fluidized bed, the relative humidity (H) and the air volume (S) supplied to the fluidized bed after heating. The temperature is calculated by the following formula from the temperature in the layer (L) during granulation, the spray rate of bound water (v), and the solid content concentration (C).
The saturated steam amount is a value at 1 atm.

Theoretical relative humidity (%) = [saturated water vapor amount at ambient temperature t (g / g) × relative humidity H (%) / 100+
Spraying speed v (g / min) x {100-solid content concentration C (%)}
/ 100 / Supply air flow rate S (g / min)] / Saturated water vapor amount at bed temperature L (g / g) × 100 Air to be supplied into the granulating device for flowing the granules in the present invention is dehumidified Preferably. Not only can the granules be manufactured with stable performance, but also the drying time can be shortened. As a method of dehumidifying, a method of once cooling the air with water or a refrigerant and then removing the moisture by dew condensation is preferably used. At this time, the cooling temperature (dehumidifying temperature) of the air is
It is preferably 20 ° C or lower. When supplying air dehumidified by this method, the theoretical relative humidity is calculated by the following equation.

Theoretical relative humidity (%) = [saturated water vapor amount at dehumidification temperature (g / g) + spraying speed v (g / min)
× {100-concentration of solid content C (%)} / 100 / air flow rate S (g
/ Min)] / Saturated water vapor amount at layer temperature L (g /
g) × 100 To spray bound water on flowing granules, pressurizing nozzle,
A rotating disk, a two-fluid nozzle or the like can be used. The pressurizing nozzle applies pressure to the bound water and ejects it as a high-speed fluid into the atmosphere to obtain fine droplets by the relative speed with the atmosphere. The rotating disk is one in which a liquid is poured into the center of a disk that is rotating at high speed, and the liquid is atomized into droplets around the disk by centrifugal force. The two-fluid nozzle utilizes a fact that a compressible gas such as air, nitrogen gas, or water vapor can obtain a high-speed air flow at a relatively low pressure, and thereby the liquid is dispersed to obtain fine droplets.

In the present invention, a method of spraying bound water with a two-fluid nozzle is preferable because the droplets dry quickly and granules suitable for compression molding are easily obtained. In this case, the ratio of the atomized air capacity discharged from the nozzle per unit time to the combined water capacity, that is, (atomized air capacity per unit time) / (combined water capacity per unit time) is defined as the gas-liquid ratio. Then, the gas-liquid ratio is 100 or more, preferably 10000 or less, particularly
It is preferably 1000 or more and 5000 or less.

In the present invention, the bound water may be a solvent alone, but is preferably a solution containing a binder and the like. As the solvent, water or a mixed solvent of water and alcohols can be adopted, but water is preferred for reasons such as influence on the processing performance of the light-sensitive material, safety and cost. As alcohols, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol,
Butyl alcohol and the like can be mentioned. The binder has a function of binding powders and granules, and for reasons such as solubility and photosensitive material processing performance, sugars, water-soluble polymers, etc., specifically sugar alcohols, monosaccharides, disaccharides, dextrins. Preferred are celluloses, celluloses, polyalkylene glycols, polyvinylpyrrolidones and the like, and sugar alcohols, dextrins and polyalkylene glycols are particularly preferred. Further, to the extent that the effects of the present invention are not impaired,
It is also possible to add an oxidizing agent, a reducing agent, an alkaline agent, a buffer agent and the like. Various additives to be contained in the bound water are easily available as commercial products.

The concentration of the additive in the bound water is preferably 1 to 60% by weight, particularly 5 to 30% by weight for reasons such as mist and granule uniformity and nozzle clogging.
Further, the total amount of the bound water sprayed is preferably 1 to 50% by weight, and particularly 5 to 25% by weight based on the charged amount of the powdery or granular material in order to obtain desired granules.

Next, the compound group contained in the solid processing composition according to the present invention will be described. The present invention is effective for granulation of a powder or granule containing at least 5% by weight of at least one selected from these compound groups.

Preferred thiosulfates are ammonium thiosulfate, sodium thiosulfate and potassium thiosulfate.

Preferred sulfites are ammonium sulfite, sodium sulfite and potassium sulfite.

Preferred bisulfites are ammonium bisulfite, sodium bisulfite, potassium bisulfite, ammonium metabisulfite, sodium metabisulfite and potassium metabisulfite.

Preferred carbonates are potassium carbonate and sodium carbonate.

Preferred as the aminopolycarboxylic acid are ferric salts of chelating agents represented by the general formulas [AI] to [A-VII].

[0035]

Embedded image

[In the formula, A _{1 to} A ₄ are each a hydrogen atom, a hydroxy group, —COOM, —PO ₃ (M ₁ ) ₂ , —CH ₂ COOM ₂ , —CH ₂ O
Represents H or a lower alkyl group. However, at least one of A _{1 to} A ₄ is —COOM, —PO ₃ (M ₁ ) ₂ , and —CH ₂ COOM ₂ .
M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ]

[0037]

Embedded image

[In the formula, A _{11 to} A ₁₄ are each —CH ₂ OH,
It represents —COOM ₃ or —PO ₃ (M ₄ ) ₂ and each of M ₃ and M ₄ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X represents an alkylene group having 2 to 6 carbon atoms or-(B ₁ O) n-B _2- , n represents an integer of 1 to 8 and B ₁
And B ₂ each represent an alkylene group having 1 to 5 carbon atoms. ]

[0039]

Embedded image

[In the formula, A _{21 to} A ₂₄ are each —CH ₂ OH,
It represents —COOM ₅ or —PO ₃ (M ₆ ) ₂ and each of M ₅ and M ₆ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. X ₁ is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring,
Or _{- (B 11 O) n 5} -B 12 - represents, n ₅ represents an integer of 1-8, respectively B ₁₁ and B ₁₂ represents an alkylene group having 1 to 5 carbon atoms. n _{1 to} n ₄ each represent an integer of 1 or more. ]

[0041]

[Chemical 4]

[Wherein R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group or an aryl group, and the alkyl group and the aryl group may be substituted. L is

[0043]

Embedded image

Y _{1 to} Y ₃ each represent an alkylene group or an arylene group, X ₂ and X ₃ each represent an oxygen atom or a sulfur atom, and R _{3 to} R ₇ each represent a hydrogen atom or an alkyl group. Represents a group or an aryl group. ]

[0045]

[Chemical 6]

[In the formula, R _{8 to} R ₁₀ are each a hydrogen atom,
It represents an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent. L is a general formula [A-I
V] is synonymous with L. W represents a divalent linking group. ]

[0047]

[Chemical 7]

[In the formula, R _{11 to} R ₁₃ and R _{16 to} R ₁₉ each represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group may have a substituent. R ₁₄
And R ₁₅ each represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfinyl group, an alkyl group or an aryl group, and the alkyl group and the aryl group. May have a substituent, and R ₁₄ and R ₁₅ may form a 5-membered ring or a 6-membered ring. A represents a carboxy group, a phosphono group, a sulfo group, a hydroxy group, or an alkyl metal salt or ammonium salt thereof.
Y represents an alkylene group or an arylene group and may have a substituent. t and u represent 0 or 1, respectively. ]

[0049]

Embedded image

[In the formula, A _{31 to} A ₃₅ are —COOM ₇ ,
Represents _{-PO 3 M 8 M 9, M} 7 ~M 9 are each a hydrogen atom, an alkali metal or ammonium ion, n ₆ is 1 or 2. Specific examples of these aminopolycarboxylic acids include the exemplified compounds AI described in JP-A-6-35151, pages 12 to 42.
-1 to 15, A-II-1 to 17, A-III-1 to 41, A-IV
-1 to 30, AV-1 to 35, A-VI-1 to 16 and diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentamethylenephosphonic acid and the like, and particularly preferred compounds are as follows. .

[0051]

[Chemical 9]

The para-phenylenediamine compound is preferably a compound having a water-soluble group. Examples of the para-phenylenediamine-based compound having a water-soluble group include those having at least one water-soluble group in the amino group of the para-phenylenediamine-based compound or on the benzene nucleus. Specific water-soluble groups include-(CH ₂ ) _n CH ₂ OH,-(CH
₂ ) _m NHSO ₂ (CH ₂ ) _n CH ₃ , − (CH ₂ ) _m O (CH ₂ ) _n CH ₃ , − (CH ₂ CH ₂ O)
_{n C m H 2m + 1,} -COOH group, -SO ₃ H groups (m and n each are. represents an integer of 0 or more), and as such are preferable.

Specific examples of the para-phenylenediamine compound preferably used in the present invention are described in JP-A No. 4-86741, pages 7 to 9 (C-1) to
(C-16), (1) to (26) described in No. 3-246543, pages 6 to 10, and the like. The color developing agent is usually used in the form of hydrochloride, sulfate, p-toluenesulfonate, or the like. The compounds preferably used are shown below.

[0054]

[Chemical 10]

[0055]

[Chemical 11]

[0056]

[Chemical 12]

[0057]

[Chemical 13]

Of these, those particularly preferably used are (C-1), (C-3), (C-17) to (C-2).
0), and more preferred are (C-1) and (C-
3).

In the present invention, the preferred hydroxylamine derivative is represented by the following general formula [B].

[0060]

Embedded image

[In the formula, R ₂₀ and R ₂₁ each represent a hydrogen atom or an alkyl group which may have a substituent. ] The alkyl group represented by R ₂₀ and R ₂₁ is preferably
It represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and particularly preferably 1 to 5 carbon atoms. As the substituent, a carboxy group, a sulfo group, a phosphono group, a sulfinic acid residue, a hydroxy group, a cyano group, an alkoxy group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, and an alkyl-substituted group. Optionally carbamoyl group, optionally substituted alkyl sulfamoyl group, optionally substituted alkylsulfonyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, arylsulfonyl group, nitro group, cyano group Alternatively, it represents a halogen atom. There may be two or more substituents. R ₂₀ and R ₂₁ are hydrogen atom, methyl group, ethyl group, propyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, methoxyethyl group, A cyanoethyl group or a hydroxyethyl group can be mentioned as a preferable example, and a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group,
A sulfopropyl group, a phosphonomethyl group, a methoxyethyl group, a cyanoethyl group or a phosphonoethyl group can be mentioned as a particularly preferable example. R ₂₀ and R ₂₁ may combine to form a ring.

The compound represented by the general formula [B] is used in the form of a usual free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate or acetate. You can When it has an anionic substituent such as a carboxyl group, a sulfo group or a phosphono group, it may be in the form of an alkali metal salt or an ammonium salt.

Typical examples of the compounds represented by the general formula [B] are shown below, but the present invention is not limited to these compounds.

[0064]

[Chemical 15]

[0065]

Embedded image

[0066]

[Chemical 17]

[0067]

Embedded image

[0068]

[Chemical 19]

[0069]

Embedded image

[0070]

[Chemical 21]

Among these, particularly preferable compounds are:

[0072]

[Chemical formula 22]

Examples include:

Next, the tablet manufacturing method of the present invention will be described.

The tablet-like solid processing agent in the present invention (hereinafter,
Also called a tablet. The term “)” refers to a solid processing agent in which at least a part of the raw material is granules, which is compression-molded into a certain shape, but it is preferably molded from only the granules in order to further exert the effects of the present invention. Further, although it is preferable to mold the granules by one kind, it may be molded by two or more kinds in order to obtain storage stability. When mixing two or more types of granules for compression molding or mixing a lubricant, it is preferable to mix them for about 5 to 10 minutes by using an ordinary mixer. The lubricant to be mixed is preferably a water-soluble surfactant because the tablet is a photographic processing agent.

The tablet-like solid processing agent can be produced by using a compressor such as a hydraulic press machine, a single-shot tableting machine, a rotary tableting machine, a briquetting machine and the like. It is advantageous in terms of productivity.

In the rotary tableting machine, the upper punch and the lower punch are aligned in a cylindrical shape by the turntable, and when the granules are filled by the hopper, the upper punch and the lower punch are pressed and compressed,
Tablets can be made continuously. The step of compressing the granules into tablets is the first step in which the upper and lower punches are compressed while approaching each other along the pressure roller, and the upper and lower punches move horizontally along the lowermost end and the uppermost end of the pressure roller, respectively. It consists of a second step and a third step of completing and releasing the compression. The time required for the first process is called the dynamic compression time, the time required for the second process is called the compression stagnation time, and both are called the total compression time. Here, if the rotation speed of the turntable becomes faster, the compression stagnation time becomes shorter, and the pressure strain inside the tablet may not be sufficiently relieved, and the tablet may expand over time. The physical properties of the granules, the tableting main pressure, the compression stagnation time, and the filling amount are set according to the performance to be imparted to the tablet, but in the present invention, it is carried out within the following range due to problems such as capping and lamination. preferable.

Preferred range Particularly preferred range Tableting main pressure 140 to 4300 kg / cm ² 700 to 2100 kg / cm ² Compression stagnation time 0.02 to 1.00 seconds 0.05 to 0.80 seconds The shape of the tablet is arbitrary, but it is handled in production. From the above point, the cylindrical shape is preferable, and its diameter is arbitrary depending on the purpose of use of the tablet, but in the present invention, the range of 10 to 35 mm is preferable.

[0079]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Operation 1) Preparation of solid processing agent for fixing color negative film Ammonium thiosulfate / sodium thiosulfate mixture (weight ratio 90/10) 60.0 kg Sodium sulfite 12.5 kg Ethylenediaminetetraacetic acid disodium 1.4 kg Anhydrous potassium carbonate 1.4 kg Each of the above compounds was pulverized with a commercially available hammer mill so that the weight average particle diameter was 50 μm to 150 μm. The obtained powder is fluidized bed granulator [manufactured by Paulec Co .; GPCG-60]
Type], set the air supply temperature to 55 ° C, and supply air volume 40m ³ /
Made to flow at min. At this time, as shown in Table 1, the supply air was dehumidified as needed. Preheat until the exhaust temperature reaches 45 ℃, then use Pine Flow (Matsuya Chemical Co., Ltd.) 20
A wt% aqueous solution was sprayed with a two-fluid nozzle. The atomizing speed at this time is as shown in Table 1, and the atomizing air was adjusted so that the gas-liquid ratio was 2700. The aqueous solution (bound water) was sprayed until it reached 10% by weight based on the charged amount of powder.
The temperature in the layer during spraying was 43 ° C. After the spraying was finished, the air supply temperature and the air flow rate were kept unchanged, and the mixture was allowed to flow for about 1 hour to be dried.

Separately, 100 kg of a mixture of ammonium thiosulfate / sodium thiosulfate (weight ratio 90/10) was used with a new speed mill (made by Okada Seiko Co., Ltd.) and the screen opening was adjusted to 0.
The size was adjusted to 5 mm. This sized product, the granules granulated as described above, and the crushed Soypon SLP (manufactured by Kawaken Fine Chemical Co., Ltd.) were mixed at a ratio of 300: 200: 1 for about 10 minutes using a commercially available cross rotary mixer.

The mixture thus obtained was used in the form of a tablet having a tablet press modified from Kikusui Seisakusho Co., Ltd. Clean Press Collect 18K to have a filling amount of 11 g per tablet and a flat-corner shape with a diameter of 30 mm. Using a pestle, the tablets were prepared by compression molding at a tableting main pressure of about 1 t / cm ² and a compression stagnation time of 0.05 seconds.

(Operation 2) Preparation of Bleaching and Fixing Agent for Color Paper 5.0 kg of sodium carbonate monohydrate was pulverized with a commercially available hammer mill until the weight average particle diameter became 50 μm or more and 150 μm or less. This and 75.0 kg of ethylenediaminetetraacetic acid monosodium trihydrate are put into a fluid bed granulator; model GPCG-60 manufactured by Powrex Co., Ltd. Granulation and drying were performed under the same conditions as in (Operation 1) except that the conditions were changed as described in 2. This is designated as Bleach-fixing agent granule A.

Ammonium thiosulfate / sodium thiosulfate mixture (weight ratio = 90: 10) 57.0 kg Sodium metabisulfite 21.8 kg Sodium carbonate monohydrate 0.7 kg Each of the above compounds had a weight average particle size of 50 μm or more by a commercially available hammer mill. , 150 μm or less, and pulverized.
The obtained powder is a fluidized bed granulator; GP manufactured by Paulec Co., Ltd.
Charge into the CG-60 type, change the dehumidification of the supply air and the spray rate of bound water as shown in Table 2, and otherwise (operation 1)
It was granulated and dried under the same conditions as in. This is designated as bleach-fixing agent granule B.

Granules A, B, powdered polyethylene glycol # 4000, ethylenediaminetetraacetic acid and crushed Soypon SLP (manufactured by Kawaken Fine Chemicals Co., Ltd.) prepared as described above were mixed at a ratio of 70: 120: 10: 10: 3: 1. Mix for about 10 minutes using a commercial cross rotary mixer.

The obtained mixture was used in a tablet press modified from Clean Press Collect 18K manufactured by Kikusui Seisakusho Co., Ltd., the filling amount per tablet was 11 g, and a flat-cylindrical die with a corner of 30 mm was used. Tableting main pressure approx. 1 t / cm ² , compression stagnation time 0.05
The tablets were prepared by compression molding in seconds.

The theoretical relative humidity in the bed of the fluidized bed granulator was calculated by the following calculation method.

The absolute water content (X) in the layer is expressed as the sum of the water content previously contained in the air to be supplied and the water content of the combined water sprayed at the time of granulation. The absolute water content (Y) in the air to be supplied is calculated from the temperature (t) and the relative humidity at the air intake port by the following equation, assuming that there is no loss during heating and blowing.

Absolute water content of supply air Y (g / g) = saturated water vapor content at temperature t (g / g) × relative humidity H (%)
/ 100 The absolute water content (Z) by spraying is based on the assumption that the bound water immediately evaporates in the layer, and is determined by the spray rate (v) of the bound water, the solid content concentration (C), and the supply air volume (S). Calculated by the formula.

Absolute water content by spraying Z (g / g) = spraying speed v (g / min) × {100−solid content concentration C (%)} / 10
0 / Supply air volume S (g / min) Since the supply air volume is usually measured as the volume per unit time (m ³ / min), air is regarded as an ideal gas with an average molecular weight of 28.8, and the gas state Convert to weight from the equation PV = nRT. P is 1 atm, V is the measured supply air volume (m ³ / mi
n) and R are gas constants of 8.2 × 10 ⁻⁵ m ³ · atm · K ⁻¹ · mol ⁻¹ , and T is the absolute temperature of the supply air temperature (Celsius temperature +273). Therefore, the supply air volume S (g / min) = the supply air volume V (m ³ / min) ×
28.8 / (8.2 × 10 ^-5 ) / air supply temperature T. For example, if the air supply temperature is 55 ° C and the air volume is 40 m ³ / min, the air supply air volume S (g / mi
n) = 40 × 28.8 / (8.2 × 10 ^-5 ) / (55 + 273) = 42830.

Theoretical relative humidity in the layer (%) = absolute water content in layer X (g / g) / saturated water vapor amount at layer temperature L 2 (g / g) × 100 = (absolute of supply air) Moisture content Y (g / g) + absolute moisture content by spraying Z (g / g)) / saturated water vapor content at layer temperature L (g / g) x 100 The calculated theoretical relative humidity is shown in Tables 1 and 2. Show.

At this time, the following evaluations were performed.

<< Ratio of Fine Powder >> 150 from the obtained granules
g was collected, classified with a JIS standard sieve having an opening of 149 μm, and the generation rate of fine powder was calculated from the weight of the passed particles.

<< Amount of coarse particles >> 150 g from the obtained granules
After sorting and classifying with a JIS standard sieve having an opening of 4000 μm, the amount of coarse particles was calculated from the weight on the sieve.

<< Variation in Filling Amount >> Tablets discharged from the tableting machine were sampled every 50 tablets, and the weight was measured to obtain the variation width with respect to the target value.

<< Expansion rate of tablets >> Ten tablets thus prepared were sealed in an aluminum packaging material laminated with polyethylene on the inside, and stored for 1 month at 50 ° C and 60% RH. Was measured.

The results of the color negative film fixing treatment agent are shown in Table 1, and the results of the color paper bleach-fixing treatment agent are shown in Table 2.
Shown in

[0098]

[Table 1]

[0099]

[Table 2]

As a result, according to the production method of the present invention, the yield of granules is good, the amount of fine powder and coarse particles generated is small, the variation during filling during compression molding into tablets is small, and the shape changes due to tablet storage. It turns out that it is excellent even in the small of. In particular, the effect of the present invention is remarkable when the relative humidity in the layer is 20% or more and 50% or less.

Example 2 In the same manner as in Experiment Nos. 1-10 and 2-10 of Example 1, except that the two-fluid nozzle was not used and atomizing air was not used and the pressure nozzle was used for atomization, the same procedure was performed. When the same evaluation was performed on the granules and tablets, it was found that the amount of coarse particles and the variation at the time of filling were deteriorated by 50% or more, and the two-fluid manufacturing method was very advantageous.

Example 3 In the operation of Experiment No. 1-10 of Example 1, the atomizing air was adjusted to set the gas-liquid ratio as shown in Table 3 to obtain a tablet-shaped color negative film fixing treatment agent. It was created and evaluated as follows. The results are shown in Table 3.

<< Reduction of Tablet Hardness >> The hardness of 10 tablets arbitrarily extracted from the prepared tablets was measured using a modified hardness tester manufactured by Okada Seiko Co., Ltd., and an average value was obtained. Another 10
The tablet was sealed in an aluminum wrapping material laminated with polyethylene and stored for 2 weeks at 50 ° C. and 60% RH, and the hardness was measured in the same manner (hardness before storage-hardness after storage) / before storage The hardness was determined as the hardness reduction rate (%).

<< Powder generation rate by vibration test >> 40 tablets prepared were stored in Konica Corporation's Eco Jet Chemical storage cartridge, and the inside was sealed with an aluminum packaging material laminated with polyethylene, then at 50 ° C. , 60%
It was stored for 1 week under the condition of RH. This sample was used for vibration tester BF-UA (made by IDEX Co., Ltd.) for 5 to 6
A vibration test was performed at 7 Hz / 10 min for 1 hour, and the powder generation rate was calculated from the weight loss rate before and after the test.

[0105]

[Table 3]

From the results shown in Table 3, it can be seen that the manufacturing method of the present invention is 2
It can be seen that when a fluid nozzle is used and the gas-liquid ratio is 100 to 10,000, there is no decrease in hardness or abrasion of the obtained tablets, which is advantageous.
If the hardness of the tablet is reduced within 30% and the powder generated by vibration is within 0.2%, there is generally no problem as a product.

Example 4 As is clear from a comparison between Experiment Nos. 1-6 and 1-9 of Example 1, when it was attempted to maintain the same relative humidity, dehumidification of the supply air resulted in a higher spray rate. It can be made large and can be granulated in a short time. Further, after the spraying was completed, the time required for the granulated product to dry to a moisture content of 1% or less was measured by a commercially available infrared moisture meter. Efficiency has improved.

Example 5 In Experiment No. 1-10 of Example 1, the number of revolutions of the hammer mill was adjusted and pulverization was performed, and the same operation was performed by using the granular material having the weight average particle diameter shown in Table 4. Table 4 shows the results of similar evaluations of the resulting tablet-like color negative film fixing treatment agent for hardness reduction and powder generation rate due to vibration.
The weight average particle diameter was calculated by the sieving method.

[0109]

[Table 4]

As a result, by setting the weight average particle diameter of the granules to be granulated to 20 to 350 μm, it is possible to prevent hardness deterioration and abrasion of the tablets obtained by compression molding, and obtain good results. Understand.

Example 6 In Experiment No. 2-10 of Example 1, the same operation was carried out except that the total amount of the bound water sprayed with respect to the charged amount of the powder was adjusted to the value shown in Table 5 to obtain tablets. A color paper bleach-fixing treatment agent was prepared and evaluated in the same manner for the decrease in hardness and the generation rate of powder due to vibration. The results are shown in Table 5.

[0112]

[Table 5]

As is clear from the results shown in Table 5, the effect of the present invention can be further exerted by setting the amount of bound water to 1.0 to 50% by weight with respect to the charged amount of powder.

Example 7 In Experiment No. 1-10 of Example 1, the same operation was performed except that the kind and concentration of the binder in the binding water to be sprayed were adjusted to the values shown in Table 6, and a tablet-like color negative was carried out. A film fixing treatment agent was prepared, the variation of the filling amount and the expansion coefficient of the tablet were evaluated in the same manner, and the results of the following evaluation of the blocking of granules are shown in Table 6.

<< Blocking of granules >> 1 kg of prepared granules
Was sealed in a polyethylene bag and stored under conditions of 25 ° C and 70% RH for 1 week, then classified with a JIS standard sieve having an opening of 4000 μm, and the amount of aggregates (blocking) on the sieve was measured. .

[0116]

[Table 6]

From this, it is understood that the effect of the present invention can be further exerted by setting the binder concentration in the bound water to be sprayed to 1.0 to 60% by weight.

[0118]

According to the present invention, thiosulfates, sulfites,
Bisulfite, ferric aminopolycarboxylic acid, carbonate,
In the case of granulating a composition containing a paraphenylenediamine color developing agent, or hydroxylamine or a derivative thereof using a fluidized bed granulator, when performing compression molding using the obtained granules, There is no variation, and it is possible to effectively prevent abrasion and expansion when forming a tablet.

[Brief description of drawings]

FIG. 1 is a schematic view of an example of a fluidized bed granulator.

[Explanation of symbols]

 1 Fluid tank body 2 Dust collection filter 3 Spray device 4 Rectifier plate A Exhaust fan B Compressed air C Liquid feeder D Heat exchanger E Air supply filter F Blower fan

Claims (10)

[Claims] 1. At least one selected from the group of compounds {thiosulfate, sulfite, bisulfite, ferric aminopolycarboxylic acid salt, carbonate, paraphenylenediamine color developing agent, hydroxylamine and its derivative}. A silver halide photograph characterized by having a theoretical relative humidity of 15% or more and 60% or less when spraying granules containing seeds in a fluid state by an air stream and using bound water A method for producing a granular solid processing agent for a light-sensitive material. 2. The production of a granular solid processing agent for a silver halide photographic light-sensitive material according to claim 1, wherein the granulation is carried out in an atmosphere having a theoretical relative humidity of 20% or more and 50% or less. Method. 3. The method for producing a granular solid processing agent for a silver halide photographic light-sensitive material according to claim 1, which is a two-fluid type spraying method. 4. When the gas-liquid ratio of the two-fluid system is defined as (volume of atomizing air supplied per unit time) / (volume of combined water supplied per unit time), the gas-liquid ratio is 100
It is above 10000, It is characterized by the above-mentioned.
Or the method for producing a granular solid processing agent for a silver halide photographic light-sensitive material as described in 3 above. 5. The method for producing a granular solid processing composition for a silver halide photographic light-sensitive material according to claim 4, wherein the gas-liquid ratio is 1,000 or more and 5,000 or less. 6. A granular solid processing agent for silver halide photographic light-sensitive material according to claim 1, wherein dehumidified air is supplied in order to flow the granular material. Manufacturing method. 7. The silver halide according to claim 1, wherein granulation is performed using a powder or granular material having a weight average particle size of 20 μm or more and 350 μm or less. A method for producing a granular solid processing agent for a photographic light-sensitive material. 8. The total amount of bound water to be sprayed with respect to the charged amount of the powder and granules is 1% by weight or more and 50% by weight or less, 1, 2, 3, 4, 5, 6. Or the method for producing the granular solid processing agent for silver halide photographic light-sensitive materials as described in 7 above. 9. The concentration of the additive in the bound water is 1% by weight or more and 60% by weight or less, 1.
2. A method for producing a granular solid processing agent for a silver halide photographic light-sensitive material as described in 2, 3, 4, 5, 6, 7 or 8. 10. A tablet-like solid processing agent for silver halide photographic light-sensitive materials, characterized by compression-molding the granular solid processing agent obtained by the above-mentioned manufacturing method with a compression stagnation time of 0.02 seconds or more and 1.0 seconds or less. Manufacturing method.